CN110234698B - Rubber composition for tire and pneumatic tire - Google Patents
Rubber composition for tire and pneumatic tire Download PDFInfo
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- CN110234698B CN110234698B CN201880007572.9A CN201880007572A CN110234698B CN 110234698 B CN110234698 B CN 110234698B CN 201880007572 A CN201880007572 A CN 201880007572A CN 110234698 B CN110234698 B CN 110234698B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
- B60C2011/0016—Physical properties or dimensions
- B60C2011/0025—Modulus or tan delta
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The present invention provides a rubber composition for a tire that provides significantly improved abrasion resistance while maintaining fuel economy, and a pneumatic tire comprising the rubber composition. The present invention relates to a rubber composition for a tire, comprising: a silane coupling agent containing an alkoxysilyl group and a sulfur atom, the alkoxysilyl group being bonded to the sulfur atom through 6 or more carbon atoms; and sulfur, wherein the rubber composition contains 1.5 parts by mass or less of sulfur per 100 parts by mass of the rubber component in the rubber composition.
Description
Technical Field
The present invention relates to a rubber composition for a tire and a pneumatic tire comprising the same.
Background
Recently, due to environmental concerns, it is desired to provide a rubber material for tires having improved properties such as fuel economy and abrasion resistance. For example, contemplated techniques for improving various properties include the use of silica and silane coupling agents to increase silica dispersibility. In particular, a formulation containing silica and bis (3-triethoxysilylpropyl) tetrasulfide has been proposed (patent document 1).
Nevertheless, in order to meet the stringent requirements for improved performance, further improvements in fuel economy and wear resistance are desired.
List of cited documents
Patent document
Patent document 1: JP 4266248B
Disclosure of Invention
Technical problem
An object of the present invention is to solve the above-described problems and to provide a rubber composition for a tire that provides significantly improved wear resistance while maintaining fuel economy, and a pneumatic tire comprising the same.
Solution to the problem
The present invention relates to a rubber composition for a tire, comprising: a silane coupling agent containing an alkoxysilyl group and a sulfur atom, the alkoxysilyl group being bonded to the sulfur atom through 6 or more carbon atoms; and sulfur, wherein the rubber composition contains 1.5 parts by mass or less of sulfur per 100 parts by mass of the rubber component in the rubber composition.
Preferably, the rubber composition contains 100 parts by mass of silica and 0.5 to 25 parts by mass of a silane coupling agent with respect to 100 parts by mass of the rubber component.
The present invention also relates to a pneumatic tire formed from the rubber composition.
Advantageous effects of the invention
The rubber composition for a tire of the present invention contains a specific silane coupling agent and a predetermined amount of sulfur. Such rubber compositions provide significantly improved abrasion resistance while maintaining fuel economy.
Detailed Description
The rubber composition for a tire of the present invention comprises: a silane coupling agent containing an alkoxysilyl group and a sulfur atom, wherein the alkoxysilyl group is bonded to the sulfur atom through 6 or more carbon atoms; and sulfur. The amount of sulfur is not more than a predetermined amount.
The present invention significantly (synergistically) improves wear resistance while maintaining fuel economy. The mechanism of the effect can be explained as follows.
In particular, when a silane coupling agent in which an alkoxysilyl group is linked to a sulfur atom through a long linking portion (hereinafter, also referred to as a spacer portion) is used, the length of the bond between the silane coupling agent and silica will be longer than that obtained when a general silane coupling agent is used. Therefore, it is considered that this longer bond can receive the stress around silica in the same manner as a spring, thereby relaxing the stress on the rubber, which makes it possible to significantly improve the abrasion resistance while maintaining the fuel economy, as compared with a general-purpose silane coupling agent.
The specific silane coupling agent having a long spacer portion of the present application is also effective for improving hardness and processability as well as improving abrasion resistance. Since the target hardness depends on the predetermined member, the hardness needs to be adjusted. The hardness can be adjusted (decreased) by various techniques such as increasing the amount of oil, decreasing the amount of sulfur, or increasing the number of kneads. However, only when the specific silane coupling agent of the present application is used, particularly when the amount of sulfur is reduced, significantly enhanced abrasion resistance can be obtained. This is probably because lowering the amount of sulfur reduces the stress concentration on the crosslinking portion.
Therefore, it is considered that by using the specific silane coupling agent of the present application while reducing the amount of sulfur, the abrasion resistance improving effect of the silane coupling agent itself and the abrasion resistance improving effect by uniform crosslinking obtained by reducing the amount of sulfur can be synergistically achieved. Further, due to the rolling resistance reducing effect of the silane coupling agent, good fuel economy can also be ensured. For these reasons, it is considered that the present invention has the effect of synergistically improving the wear resistance while maintaining excellent fuel economy.
The rubber composition contains a silane coupling agent containing an alkoxysilyl group and a sulfur atom, wherein the alkoxysilyl group is bonded to the sulfur atom through 6 or more carbon atoms.
The silane coupling agent may be, for example, an organosilicon compound represented by the following average composition formula (I) and having a ratio of the number of sulfur atoms/the number of silicon atoms of 1.0 to 1.5:
wherein x represents the average number of sulfur atoms; m represents an integer of 6 to 12; and, R1～R6Identical or different and each represents a C1-C6 alkyl or alkoxy radical, R1～R3And R4～R6Is alkoxy, provided that for R1～R6The alkyl or alkoxy groups of (a) may be combined to form a ring structure.
The inventor finds that: when the organosilicon compound represented by the formula (I) is used as a silane coupling agent in a rubber composition containing an inorganic filler, the rubber composition provides good fuel economy (low heat build-up) and further achieves an improved balance of processability, which is a disadvantage of silica-containing formulations, and abrasion resistance, which is against the fuel economy.
The reason for this effect is not clear, but seems to be as follows.
The organosilicon compound (silane coupling agent) crosslinks the silica with the rubber. In particular, when the compound represented by the formula (I) having 6 to 12 carbon atoms between a sulfur atom and a silicon atom is used as the silane coupling agent, the length of the bond between silica and rubber will be longer than that obtained when a general silane coupling agent is used. Therefore, it is considered that a certain degree of flexibility is imparted to the crosslinked portion, thereby contributing to relaxation of external stress that may cause rubber failure. For this reason, it is considered that the abrasion resistance is improved as compared with the general silane coupling agent. Further, it is considered that when the number of carbon atoms between silicon and sulfur is increased as compared with a general silane coupling agent, the rate of silylation will be slightly decreased, so that excessive bonding between silica and rubber can be suppressed during kneading, and also good processability is obtained. Therefore, the wear resistance is significantly improved while maintaining good fuel economy. In addition, good processability is obtained, so that a balanced improvement of these properties can be achieved.
The symbol x represents the average number of sulfur atoms in the organosilicon compound. This means that the organosilicon compound represented by the average compositional formula (I) is a mixture of compounds having different sulfur numbers, and x is the average number of sulfur atoms of the organosilicon compound contained in the rubber composition. The symbol x is defined as {2 × (the number of sulfur atoms) }/(the number of silicon atoms). From the viewpoint of fuel economy and abrasion resistance, x is preferably 2.0 to 2.4, and more preferably 2.0 to 2.3. In particular, when x is less than the upper limit, the increase in the Mooney viscosity of the unvulcanized rubber can be suppressed, and good processability can be obtained. The number of sulfur atoms and the number of silicon atoms were measured by the following methods: the amount of sulfur or the amount of silicon in the composition was determined by X-ray fluorescence analysis and then calculated based on their molecular weights.
The symbol m represents an integer of 6 to 12, preferably 6 to 10, and more preferably 8. In this case, the above-described effects can be obtained, and the effects of the present invention can be sufficiently obtained.
Alkyl (R) from the viewpoint of fuel economy and abrasion resistance1～R6) Preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group may be linear, branched or cyclic. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
Alkoxy group (R) from the viewpoint of fuel economy and abrasion resistance1～R6) Preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. The hydrocarbon group in the alkoxy group may be linear, branched or cyclic. Specific examples thereof include methoxy group, ethoxy group, n-propoxy group, isopropoxy group and n-butoxy group.
R1～R3And R4～R6At least one of which is a C1-C6 alkoxy group. Preferably, R1～R3Two or more of (1) and R4～R6Two or more of them are alkoxy groups.
For R1～R6The C1-C6 alkyl or alkoxy groups of (A) may be joined to form a ring structure. For example, (i) when R is to be1With ethoxy radicals as R2When the methyl groups of (i) are bonded to form a ring structure, and (ii) when R is a group1With as R2When the methyl groups of (2) are bonded to form a ring structure, R1And R2The following divalent groups are formed, respectively: -O-C2H4-CH2-and-C2H4-CH2-, they are bonded to Si.
The ratio of the number of sulfur atoms to the number of silicon atoms in the organosilicon compound is 1.0 to 1.5. In other words, the ratio of the total number of sulfur atoms/the total number of silicon atoms of the organosilicon compound represented by the average compositional formula (I) contained in the rubber composition falls within the above range.
From the viewpoint of fuel economy and abrasion resistance, the ratio of the number of sulfur atoms/the number of silicon atoms is preferably 1.0 to 1.2, and more preferably 1.0 to 1.15.
The organosilicon compound represented by the average composition formula (I) wherein the ratio of the number of sulfur atoms to the number of silicon atoms is within a predetermined range can be produced, for example, by the following method.
The organosilicon compound can be prepared by reacting a halogen-containing organosilicon compound represented by the following formula (I-1) with Na2Anhydrous sodium sulfide indicated by S and optionally sulfur are reacted to produce:
wherein R is1～R3And m is as defined above, and X represents a halogen atom.
Examples of X (halogen atom) include Cl, Br and I.
Examples of the silane coupling agent (such as an organosilicon compound containing a sulfur chain) represented by the average composition formula (I) include the following compounds:
(CH3O)3Si-(CH2)6-S1-(CH2)6-Si(OCH3)3
(CH3O)3Si-(CH2)6-S2-(CH2)6-Si(OCH3)3
(CH3O)3Si-(CH2)6-S3-(CH2)6-Si(OCH3)3
(CH3CH2O)3Si-(CH2)6-S1-(CH2)6-Si(OCH2CH3)3
(CH3CH2O)3Si-(CH2)6-S2-(CH2)6-Si(OCH2CH3)3
(CH3CH2O)3Si-(CH2)6-S3-(CH2)6-Si(OCH2CH3)3
(CH3CH2O)2(CH3)Si-(CH2)6-S2-(CH2)6-Si(CH3)(OCH2CH3)2
CH3CH2O(CH3)2Si-(CH2)6-S2-(CH2)6-Si(CH3)2OCH2CH3
(CH3O)3Si-(CH2)8-S1-(CH2)8-Si(OCH3)3
(CH3O)3Si-(CH2)8-S2-(CH2)8-Si(OCH3)3
(CH3O)3Si-(CH2)8-S3-(CH2)8-Si(OCH3)3
(CH3CH2O)3Si-(CH2)8-S1-(CH2)8-Si(OCH2CH3)3
(CH3CH2O)3Si-(CH2)8-S2-(CH2)8-Si(OCH2CH3)3
(CH3CH2O)3Si-(CH2)8-S3-(CH2)8-Si(OCH2CH3)3
(CH3CH2O)2(CH3)Si-(CH2)8-S2-(CH2)8-Si(CH3)(OCH2CH3)2
CH3CH2O(CH3)2Si-(CH2)8-S2-(CH2)8-Si(CH3)2OCH2CH3
(CH3O)3Si-(CH2)11-S1-(CH2)11-Si(OCH3)3
(CH3O)3Si-(CH2)11-S2-(CH2)11-Si(OCH3)3
(CH3O)3Si-(CH2)11-S3-(CH2)11-Si(OCH3)3
(CH3CH2O)3Si-(CH2)11-S1-(CH2)11-Si(OCH2CH3)3
(CH3CH2O)3Si-(CH2)11-S2-(CH2)11-Si(OCH2CH3)3
(CH3CH2O)3Si-(CH2)11-S3-(CH2)11-Si(OCH2CH3)3
(CH3CH2O)2(CH3)Si-(CH2)11-S2-(CH2)11-Si(CH3)(OCH2CH3)2
CH3CH2O(CH3)2Si-(CH2)11-S2-(CH2)11-Si(CH3)2OCH2CH3。
examples of the halogen-containing organosilicon compound represented by the formula (I-1) include the following compounds:
(CH3O)3Si-(CH2)6-Cl
(CH3O)3Si-(CH2)6-Br
(CH3CH2O)3Si-(CH2)6-Cl
(CH3CH2O)3Si-(CH2)6-Br
(CH3CH2O)2(CH3)Si-(CH2)6-CI
CH3CH2O(CH3)2Si-(CH2)6-Cl
(CH3O)3Si-(CH2)8-Cl
(CH3O)3Si-(CH2)8-Br
(CH3CH2O)3Si-(CH2)8-Cl
(CH3CH2O)3Si-(CH2)8-Br
(CH3CH2O)2(CH3)Si-(CH2)8-Cl
CH3CH2O(CH3)2Si-(CH2)8-Cl
(CH3O)3Si-(CH2)11-Cl
(CH3O)3Si-(CH2)11-Br
(CH3CH2O)3Si-(CH2)11-Cl
(CH3CH2O)3Si-(CH2)11-Br
(CH3CH2O)2(CH3)Si-(CH2)11-Cl
CH3CH2O(CH3)2Si-(CH2)11-CI。
in the above reaction, sulfur may be optionally added to adjust the sulfur chain. The amount added may be selected according to the amount of the compound represented by formula (I-1) and the amount of anhydrous sodium sulfide to provide a desired average composition of the compound represented by formula (I).
For example, when it is desired to produce a compound represented by the average composition formula (I) (wherein x is 2.2), 1.0mol of anhydrous sodium sulfide, 1.2mol of sulfur and 2.0mol of a compound represented by the formula (I-1) may be reacted.
The above reaction may be carried out in a solvent or without a solvent. Examples of solvents that may be used include: aliphatic hydrocarbons such as pentane and hexane; aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as tetrahydrofuran, diethyl ether and dibutyl ether; and alcohols such as methanol and ethanol. Among them, the above reaction is preferably carried out in an ether (such as tetrahydrofuran) or an alcohol (such as methanol or ethanol).
The temperature during the reaction is not particularly limited, and may be room temperature to about 200 ℃, particularly preferably 60 to 170 ℃, and more preferably 60 to 100 ℃. The reaction time is more than 30 minutes, and the reaction will be completed in about 2-15 hours.
In the present invention, the solvent (if used) may be evaporated under reduced pressure after the completion of the reaction, before or after removing the formed salt by filtration.
The silane coupling agent may be, for example, a commercially available product of Degussa (Degussa), Momentive, shin-Etsu Silicone K.K., Tokyo Kasei K.K., AZmax, or Dow Corning Tokyo K.K., a silane coupling agent,
The amount of the silane coupling agent is preferably 0.5 parts by mass or more, more preferably 3 parts by mass or more, and still more preferably 6 parts by mass or more, relative to 100 parts by mass of silica. When the amount is 0.5 parts by mass or more, chemical bonding between the rubber and the silica via the silane coupling agent can be sufficiently formed, so that good silica dispersibility can be obtained, thereby improving fuel economy and abrasion resistance. The amount of the silane coupling agent is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 15 parts by mass or less. When the amount is 25 parts by mass or less, good workability can be ensured.
The rubber composition contains a prescribed amount of sulfur (sulfur crosslinking agent).
Examples of sulfur as the crosslinking agent include those commonly used in the rubber industry, such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersible sulfur, and soluble sulfur. These may be used alone, or two or more of them may be used in combination.
The sulfur may be, for example, commercially available from Hello chemical industries, Kutzu sulfur, Kabushiki Kaisha, Flexsys, Nippon Dry industries, or Mitsui chemical industries.
The amount of sulfur is 1.5 parts by mass or less, preferably 1.3 parts by mass or less, and more preferably 1.2 parts by mass or less, per 100 parts by mass of the rubber component. When the amount is 1.5 parts by mass or less, the wear resistance can be improved. The lower limit of the amount of sulfur is preferably 0.3 parts by mass or more, and more preferably 0.5 parts by mass or more. When the amount is not less than the lower limit, a predetermined hardness can be obtained and various rubber physical properties can be secured.
Examples of materials that can be used as the rubber component in the rubber composition include: diene-based rubbers such as isoprene-based rubber, polybutadiene rubber (BR), Styrene Butadiene Rubber (SBR), and styrene-isoprene-butadiene rubber (SIBR); neoprene (CR), acrylonitrile butadiene rubber (NBR), and butyl rubber (IIR). Examples of the isoprene-based rubber include: natural Rubber (NR), polyisoprene rubber (IR), modified NR (e.g., deproteinized natural rubber (DPNR), highly purified natural rubber (upnp NR)), modified NR (e.g., Epoxidized Natural Rubber (ENR), Hydrogenated Natural Rubber (HNR), grafted natural rubber), and modified IR (e.g., epoxidized polyisoprene rubber, hydrogenated polyisoprene rubber, grafted polyisoprene rubber). These rubbers may be used alone, or two or more of these may be used in combination. Among these, SBR, isoprene-based rubber and BR are preferable in order to obtain the effect of the present invention well, and SBR and/or BR are more preferable.
Any SBR may be used, including emulsion polymerized SBR (E-SBR) and solution polymerized SBR (S-SBR). Any BR can be used, including high cis 1, 4-polybutadiene rubber (high cis BR), polybutadiene rubber containing 1, 2-syndiotactic polybutadiene crystals (SPB-containing BR), and BR synthesized using rare earth catalysts (rare earth-catalyzed BR). SBR and BR may be modified SBR and modified BR, respectively, wherein the backbone or chain ends, or both, may be modified. Examples of modifying groups include nitrogen-containing groups that will interact with or react with silica.
The SBR may be, for example, a solution polymerization SBR manufactured or sold by sumitomo chemical co., JSR co., asahi chemical co., ltd.asahi or japanese ruing corporation.
The amount of SBR is preferably 20 mass% or more, more preferably 50 mass% or more, and still more preferably 60 mass% or more, based on 100 mass% of the rubber component. When the amount is 20% by mass or more, good wear resistance tends to be obtained. The amount is preferably 95% by mass or less, and more preferably 90% by mass or less. When the amount is 95% by mass or less, good low heat buildup tends to be obtained.
BR can be, for example, a commercially available product of Utsuki Kagaku K.K., JSR Kabushiki Kaisha, Asahi Kasei K.K., or Nippon Ruiki Kabushiki Kaisha.
The amount of BR is preferably 5% by mass or more, more preferably 10% by mass or more, based on 100% by mass of the rubber component. When the amount is 5% by mass or more, good wear resistance tends to be obtained. The amount is preferably 50% by mass or less, and more preferably 30% by mass or less. When the amount is 50% by mass or less, good grip performance tends to be obtained.
In order to obtain good fuel economy and good abrasion resistance, the rubber composition preferably contains silica. Examples of the silica include: dry silica (anhydrous silica) and wet silica (hydrous silica). Wet silica is preferred because it contains a large number of silanol groups.
The silica may be, for example, a commercially available product of degussa corporation, rodia corporation, tokyo silicon corporation, sovley Japan (Solvay Japan) corporation, or Tokuyama corporation.
Nitrogen adsorption of silicon dioxideSpecific surface area (N)2SA) is preferably 70m2A value of at least one of,/g, more preferably 150m2More than g. In the N2SA 70m2Above/g, abrasion resistance and other properties tend to be improved. N of silica2SA is preferably 500m2A ratio of not more than 200 m/g, more preferably2The ratio of the carbon atoms to the carbon atoms is less than g. In the N2SA 500m2At a value of/g or less, the processability tends to be improved.
The nitrogen adsorption specific surface area of silica was measured by the BET method in accordance with ASTM D3037-81.
The amount of silica is preferably 5 parts by mass or more, more preferably 30 parts by mass or more, and still more preferably 60 parts by mass or more, relative to 100 parts by mass of the rubber component. When the amount is 5 parts by mass or more, fuel economy and other properties tend to be improved. The amount is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and still more preferably 130 parts by mass or less. When the amount is more than 200 parts by mass, the balance of processability and fuel economy tends to deteriorate.
The rubber composition may contain other inorganic fillers than silica, such as calcium carbonate, calcium silicate, magnesium oxide, aluminum oxide, alumina, hydrated aluminum oxide, aluminum hydroxide, magnesium oxide, barium sulfate, talc, and mica. The total amount of the inorganic filler including silica and other inorganic fillers may be suitably within the above range.
From the viewpoint of abrasion resistance and other properties, the rubber composition preferably contains carbon black. Examples of carbon blacks include grades N110, N220, N330, and N550 carbon blacks.
The Carbon black may be, for example, a commercially available product of Asahi Carbon Co., Ltd, Kabet Japan K.K., Toshidi Carbon Co., Ltd, Mitsubishi chemical Co., Ltd, Shiwang Carbon Co., Ltd, or Columbia Carbon Co., Ltd.
Nitrogen adsorption specific surface area (N) of carbon black2SA) is preferably 70m2A value of at least one of,/g, more preferably 90m2More than g. The N is2SA is preferably 150m2A ratio of 130m or less per gram2The ratio of the carbon atoms to the carbon atoms is less than g. In the N2SA above the lower limitGood wear resistance tends to be obtained. In the N2When SA is below the upper limit, good carbon black dispersion tends to be obtained, resulting in excellent fuel economy.
N of carbon black2SA can be determined according to JIS K6217-2: 2001, measurement.
The amount of carbon black is preferably 1 part by mass or more, and more preferably 3 parts by mass or more, per 100 parts by mass of the rubber component. The amount is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 8 parts by mass or less. When the amount is 1 part by mass or more, good wear resistance tends to be obtained. When the amount is 15 parts by mass or less, good fuel economy tends to be obtained.
Preferably, the rubber composition contains a solid resin (a resin that is solid at room temperature (25 ℃). Examples of the solid resin include aromatic vinyl polymers such as α -methylstyrene resins prepared by polymerizing α -methylstyrene and/or styrene. Preferably, the solid resin has a softening point of 60 to 120 ℃. Softening point of solid resin according to JISK 6220-1: 2001, measured using a ball-and-ring softening point measuring device, and defined as the temperature at which the ball falls.
Preferred examples of the α -methylstyrene-based resin include: homopolymers of alpha-methylstyrene or styrene, and copolymers of alpha-methylstyrene and styrene, with copolymers of alpha-methylstyrene and styrene being more preferred.
The amount of the solid resin is preferably 3 to 30 parts by mass, more preferably 5 to 20 parts by mass, per 100 parts by mass of the rubber component. The incorporation of such a prescribed amount of solid resin tends to improve abrasion resistance and other properties.
The solid resin may be, for example, a commercially available product of Wanshan petrochemical Co., Ltd, Sumitomo Bakelite Co., Ltd, Anyuan Chemical Co., Tosoh Kao, Ratger Chemical (Rutgers Chemicals), BASF, Arizona Chemical (Arizona Chemical), Rikkai Chemical Co., Ltd, Japanese catalyst Co., Ltd, JX energy Co., Ltd, Mitsuwa Chemical Co., Ltd, or Tiangang Chemical industry Co., Ltd.
Preferably, the rubber composition contains oil.
Examples of oils include process oils, vegetable fats and mixtures thereof. Examples of the process oil include paraffin process oils, aromatic process oils, and naphthene process oils. Examples of the vegetable fats and oils include: castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, peanut oil, rosin, pine oil, pine tar, tall oil, corn oil, rice bran oil (rice oil), safflower oil, sesame oil, olive oil, sunflower oil, palm kernel oil, camellia oil, jojoba oil, macadamia nut oil, and tung oil. Among these, the process oil is preferred.
The oil may be, for example, a commercially available product of shinning Corporation, Sanko Industrial Co., Ltd, Japan Energy Corporation (Japan Energy Corporation), Olisoy Corporation, H & R Corporation, Fengkou oil Co., Ltd, Showa Shell oil Co., Ltd, or Fuji oil Co., Ltd.
The amount of the oil is preferably 1 part by mass or more, and more preferably 3 parts by mass or more, relative to 100 parts by mass of the rubber component. The amount is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less. When the amount is within the above numerical range, the effects of the present invention tend to be more obtained.
The amount of oil includes the amount of oil contained in the rubber (oil-extended rubber).
Preferably, the rubber composition contains a wax.
Non-limiting examples of waxes include: petroleum-based waxes such as paraffin wax and microcrystalline wax; natural waxes such as vegetable waxes and animal waxes; and synthetic waxes such as polymers of ethylene, propylene, or other monomers. In order to obtain the effects of the present invention more favorably, petroleum-based waxes are preferable, and paraffin waxes are more preferable.
The wax may be, for example, a commercially available product of Dai-Neissimal chemical industries, Japan wax Seika, or Seiko chemical industries.
The amount of the wax is preferably 1.0 part by mass or more, and more preferably 1.5 parts by mass or more, per 100 parts by mass of the rubber component. The amount is preferably 10 parts by mass or less, and more preferably 7 parts by mass or less. When the amount is within the above numerical range, the effects of the present invention tend to be well obtained.
Preferably, the rubber composition contains an antioxidant.
Examples of antioxidants include: naphthylamine-based antioxidants such as phenyl-alpha-naphthylamine; diphenylamine-based antioxidants such as octylated diphenylamine and 4, 4 '-bis (α, α' -dimethylbenzyl) diphenylamine; p-phenylenediamine antioxidants such as N-isopropyl-N ' -phenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl) -N ' -phenyl-p-phenylenediamine, and N, N ' -di-2-naphthyl-p-phenylenediamine; quinoline-based antioxidants such as 2, 2, 4-trimethyl-1, 2-dihydroquinoline polymer; monophenol-based antioxidants such as 2, 6-di-t-butyl-4-methylphenol and styrenated phenol; and bisphenol type antioxidants, triphenol type antioxidants or polyphenol type antioxidants such as tetrakis- [ methylene-3- (3 ', 5 ' -di-t-butyl-4 ' -hydroxyphenyl) propionate ] methane. Among these, p-phenylenediamine antioxidants are preferred, and among them, N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine is more preferred.
The antioxidant may be, for example, a commercially available product from Seiko chemical Co., Ltd., Sumitomo chemical Co., Ltd., New England chemical Co., Ltd., or Furex (Flexsys) Co., Ltd.
The amount of the antioxidant is preferably 1 part by mass or more, and more preferably 3 parts by mass or more, per 100 parts by mass of the rubber component. The amount is preferably 10 parts by mass or less, and more preferably 7 parts by mass or less. When the amount is within the above numerical range, the effects of the present invention tend to be well obtained.
Preferably, the rubber composition contains stearic acid.
The stearic acid may be a conventional stearic acid, and is commercially available from Nichikoku Kogyo, NOF Corp, Kao, Wako pure chemical industries, Ltd., or kokuba fatty acid Co.
The amount of stearic acid is preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more, per 100 parts by mass of the rubber component. The amount is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less. When the amount is within the above numerical range, the effects of the present invention tend to be well obtained.
Preferably, the rubber composition contains zinc oxide.
The zinc oxide may be a conventional zinc oxide, and is commercially available from mitsui metal mining co, tokyo lead corporation, white water science co (HakusuiTech co., Ltd.), regular chemical industry co.
The amount of zinc oxide is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the rubber component. The amount is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less. When the amount is within the above numerical range, the effects of the present invention tend to be more obtained.
Preferably, the rubber composition contains a vulcanization accelerator.
Examples of the vulcanization accelerator include: thiazole-based vulcanization accelerators such as 2-mercaptobenzothiazole, di-2-benzothiazyl disulfide and N-cyclohexyl-2-benzothiazylsulfenamide; thiuram-based vulcanization accelerators such as tetramethylthiuram disulfide (TMTD), tetrabenzylthiuram disulfide (TBzTD) and tetrakis (2-ethylhexyl) thiuram disulfide (TOT-N); sulfenamide-based vulcanization accelerators such as N-cyclohexyl-2-benzothiazolesulfenamide, N-tert-butyl-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide and N, N' -diisopropyl-2-benzothiazolesulfenamide; and guanidine-based vulcanization accelerators such as diphenylguanidine, diorthotolylguanidine and orthotolylguanidine. Among these, sulfenamide-based vulcanization accelerators and/or guanidine-based vulcanization accelerators are preferable in order to more suitably obtain the effects of the present invention.
The vulcanization accelerator may be, for example, a commercially available product of Dainippon chemical industries, Ltd or Sanxin chemical industries.
The amount of the vulcanization accelerator is preferably 1 part by mass or more, and more preferably 3 parts by mass or more, per 100 parts by mass of the rubber component. The amount is preferably 10 parts by mass or less, and more preferably 7 parts by mass or less. When the amount is within the above numerical range, the effects of the present invention tend to be well obtained.
In addition to the above-mentioned ingredients, the rubber composition may contain additives commonly used in the tire industry. Examples thereof include: an organic peroxide; and processing aids such as plasticizers and lubricants.
The rubber composition of the present invention can be produced by a known method. For example, the rubber composition can be produced by the following method: the above-mentioned components are kneaded using a rubber kneading apparatus such as an open roll mill or a Banbury mixer, and the kneaded mixture is vulcanized. In particular, since the silane coupling agent specified herein having a long spacer portion slowly reacts with silica, it is considered that kneading for a long time allows the reaction between the silane coupling agent and silica to sufficiently proceed to increase the amount of silica organizing (organization), so that silica dispersibility can be further improved. Therefore, the rubber composition has the effect of improving not only abrasion resistance but also fuel economy and processability, achieving an overall improvement in the balance of these properties.
The rubber composition of the present invention can be suitably used in various tire components such as: sidewall, tread (tread running surface), tread base, undertread, bridge apex (clinch apex), bead apex, breaker cushion rubber (breaker cushion rubber), carcass cord rubberized rubber, insulation, chafer and inner liner; and a side reinforcing layer of the run-flat tire. Among them, the rubber composition can be suitably used in a tread (cap tread) because of its good fuel economy and wear resistance.
The pneumatic tire of the present invention can be manufactured by a conventional method using the rubber composition. Specifically, an unvulcanized rubber composition containing various additives as required may be extruded into the shape of a tire member (such as a tread), and then formed and assembled with other tire members in a conventional manner on a tire building machine to manufacture an unvulcanized tire, which is then heated and pressurized in a vulcanizing machine to prepare a tire.
The tire of the present invention is suitable for use as, for example, a passenger tire, a truck tire or a two-wheeled vehicle tire, a high performance tire or a racing tire.
Examples
The chemicals used in examples and comparative examples are listed below.
NR：TSR
SBR: unmodified solution-polymerized SBR (extender oil content: 37 parts by mass/(100 parts by mass of rubber), styrene content: 40 parts by mass, vinyl content: 25% by mass, Mw: 1,200,000)
BR: unmodified solution-polymerized BR (cis content: 96 mass%, vinyl content: 2 mass%)
Silicon dioxide: n is a radical of2SA 175m2/g
Carbon black N220: n is a radical of2SA 111m2/g
Silane coupling agent 1: silane coupling agent synthesized in production example 1 described below
Silane coupling agent 2: si266 (a compound represented by the following formula, wherein x is 2.2) from winning creative goods company
Silane coupling agent 3: silane coupling agent synthesized in production example 2 below
Silane coupling agent 4: silane coupling agent synthesized in production example 3 described below
Silane coupling agent 5: silane coupling agent synthesized in production example 4 described below
Oil: paraffin series operating oil
Resin: alpha-methylstyrene series resin (copolymer of alpha-methylstyrene and styrene, softening point: 85 ℃, Tg: 43 ℃ C.)
Zinc oxide: zinc oxide #1 from Mitsui Metal mining corporation
Stearic acid: stearic acid "TSUBAKI" purchased from Nissan oil Co., Ltd "
Wax: paraffin wax
Antioxidant: n- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine
Sulfur: powdered sulfur from Hejian chemical industries, Ltd
Vulcanization accelerator 1: n-tert-butyl-2-benzothiazolesulfenamides
Vulcanization accelerator 2: diphenylguanidine
Production example 1 Synthesis of silane coupling agent 1 (x ═ 2.2, m ═ 8, R1～R6＝OCH2CH3))
To a 2L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer were charged 78.0g (1.0mol) of anhydrous sodium sulfide, 38.5g (1.2mol) of sulfur and 480g of ethanol, followed by heating to 80 ℃. To the mixture obtained 622g (2.0mo1) of 8-chlorooctyltriethoxysilane were added dropwise, followed by heating at 80 ℃ for 10 hours with stirring. The reaction solution was pressure-filtered through a filter plate to obtain a filtrate from which salts formed by the reaction were removed. The filtrate was heated to 100 ℃, and ethanol was evaporated under reduced pressure of 10mmHg or less, to obtain silane coupling agent 1 as a reaction product.
The silane coupling agent 1 compound has: a sulfur content of 10.8 mass% (0.34mol), a silicon content of 8.7 mass% (0.31mol), and a ratio of the number of sulfur atoms/the number of silicon atoms of 1.1.
Production example 2 Synthesis of silane coupling agent 3 (x: 2.0, m: 8, R)1～R6＝OCH2CH3))
Silane coupling agent 3 as a reaction product was produced by the same synthetic procedure as in production example 1 except that: the amount of sulfur was changed to 32.1g (1.0 mol).
The silane coupling agent 3 compound has: a sulfur content of 10.0 mass% (0.31mol), a silicon content of 8.8 mass% (0.31mol), and a ratio of the number of sulfur atoms/the number of silicon atoms of 1.0.
Production example 3 Synthesis of silane coupling agent 4 (x. is 2.4, m. is 8, R)1～R6＝OCH2CH3))
A silane coupling agent 4 as a reaction product was produced by the same synthetic procedure as in production example 1 except that: the amount of sulfur was changed to 45.0g (1.4 mol).
The silane coupling agent 4 compound has: a sulfur content of 11.9 mass% (0.37mol), a silicon content of 8.7 mass% (0.31mol), and a ratio of the number of sulfur atoms/the number of silicon atoms of 1.2.
Production example 4 Synthesis of silane coupling agent 5 (x. is 2.2, m. is 8, R)1、R2、R4、R5＝OCH2CH3，R3、R6＝CH3))
Silane coupling agent 5 as a reaction product was produced by the same synthetic procedure as in production example 1 except that: 562g (2.0mol) of 8-chlorooctyldiethoxymethylsilane were used instead of 8-chlorooctyltriethoxysilane.
The silane coupling agent 5 compound has: a sulfur content of 11.0 mass% (0.34mol), a silicon content of 8.7 mass% (0.31mol), and a ratio of the number of sulfur atoms/the number of silicon atoms of 1.1.
< examples and comparative examples >
(first step)
Materials other than sulfur and a vulcanization accelerator were charged into a banbury mixer and kneaded according to the respective formulations shown in table 1 or table 2 to produce a first kneaded mixture. During the kneading, after the rubber temperature reached the preset reaction temperature, the rubber temperature was adjusted to the reaction temperature. + -. 3 ℃. Once a predetermined period of time (reaction time) has elapsed, kneading is stopped. The reaction temperature and the reaction time in each example are shown in table 1 or table 2.
(second step)
The first kneaded mixture was introduced into a banbury mixer and further kneaded to produce a second kneaded mixture. This kneading is carried out under the same conditions as in the first step.
(third step)
The second kneaded mixture, sulfur and a vulcanization accelerator were introduced into an open roll mill and kneaded to produce an unvulcanized rubber composition. Kneading was stopped once the rubber temperature reached 110 ℃. The kneading time was 5 minutes.
(vulcanization step)
The unvulcanized rubber composition was molded into a tread shape and assembled with other tire components on a tire building machine, followed by press vulcanization at a temperature of 170 ℃ for 20 minutes to manufacture a tire for test (tire size: 11X 7.10-5).
The test tires produced as described above were evaluated as follows. Tables 1 and 2 show the results. Comparative example 1-1 was used as a reference for comparison of examples 1-1 to 1-10 and comparative examples 1-1 to 1-3. Comparative example 2-1 was used as a reference for comparison between example 2-1 and comparative example 2-1.
(abrasion resistance)
The amount of wear (decrease) of the sample taken out from each test tire tread was measured using a Lambourn wear tester under conditions of room temperature, an applied load of 1.0kgf, and a slip ratio of 30%. The measurement results were expressed as an index using the following formula. Higher index indicates better abrasion resistance.
(abrasion resistance index) × 100 (abrasion loss of reference comparative example)/(abrasion loss of each formulation example)
(fuel economy)
The loss tangent (tan. delta.) at 60 ℃ of the sample obtained from each test tire tread was measured using a viscoelastometer (available from Kaisha, Ltd.) under conditions of an initial strain of 10%, a dynamic strain of 2% and a frequency of 10 Hz. The tan δ value is expressed as an index using the following formula, in which the reference comparative example is set to 100. A higher index indicates better fuel economy.
(fuel economy index) ═ tan δ of reference comparative example)/(tan δ of each formulation example) × 100
[ Table 1]
[ Table 2]
As shown in tables 1 and 2, compositions having both features (i.e., use of the specific silane coupling agents herein and reduction of the amount of sulfur) also exhibit significantly improved wear resistance while maintaining good fuel economy. In particular, comparison of comparative examples 1-1 to 1-3 with example 1-1 shows that the use of these two features synergistically improves the wear resistance, and the average performance of wear resistance and fuel economy.
Claims (3)
1. A rubber composition for a tire, comprising:
a silane coupling agent containing an alkoxysilyl group and a sulfur atom, the alkoxysilyl group being bonded to the sulfur atom through 6 or more carbon atoms; and
the sulfur is added to the reaction mixture in a solvent,
the silane coupling agent is an organosilicon compound represented by the following average composition formula (I) and having a ratio of the number of sulfur atoms to the number of silicon atoms of 1.0 to 1.5:
wherein x represents the average number of sulfur atoms; m represents an integer of 6 to 10; and R1～R6Identical or different and each represents a C1-C6 alkyl or alkoxy radical, R1～R3And R4～R6Is alkoxy, provided that for R1～R6The alkyl or alkoxy groups of (a) may be combined to form a ring structure,
the rubber composition contains 1.5 parts by mass or less of sulfur per 100 parts by mass of the rubber component in the rubber composition.
2. The rubber composition for a tire according to claim 1,
wherein the rubber composition comprises 100 parts by mass of silica and 0.5-25 parts by mass of a silane coupling agent, relative to 100 parts by mass of a rubber component.
3. A pneumatic tire formed from the rubber composition of claim 1 or 2.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017017713 | 2017-02-02 | ||
| JP2017-017713 | 2017-02-02 | ||
| PCT/JP2018/002609 WO2018143111A1 (en) | 2017-02-02 | 2018-01-29 | Rubber composition for tires, and pneumatic tires |
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| CN110234698A CN110234698A (en) | 2019-09-13 |
| CN110234698B true CN110234698B (en) | 2022-06-24 |
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| CN201880007572.9A Active CN110234698B (en) | 2017-02-02 | 2018-01-29 | Rubber composition for tire and pneumatic tire |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US11124632B2 (en) |
| EP (1) | EP3567078A4 (en) |
| JP (1) | JP7024712B2 (en) |
| CN (1) | CN110234698B (en) |
| WO (1) | WO2018143111A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113710739A (en) * | 2019-05-28 | 2021-11-26 | 花王株式会社 | Additive for rubber |
| CN111233916A (en) * | 2020-02-06 | 2020-06-05 | 南京曙光精细化工有限公司 | Long carbon chain sulfur-containing silane coupling agent, and preparation method and application thereof |
| CN115175818B (en) * | 2020-10-07 | 2023-04-11 | 住友橡胶工业株式会社 | Tyre for vehicle wheels |
| DE102020215465A1 (en) | 2020-12-08 | 2022-06-09 | Continental Reifen Deutschland Gmbh | Sulfur crosslinkable rubber compound, vulcanizate and vehicle tires |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5994448A (en) * | 1998-08-12 | 1999-11-30 | The Goodyear Tire & Rubber Company | High performance tire tread rubber composition |
| US6053226A (en) * | 1998-03-13 | 2000-04-25 | The Goodyear Tire & Rubber Company | Rubber composition reinforced with silica and tire with tread thereof |
| JP2001226532A (en) * | 1999-12-08 | 2001-08-21 | Dow Corning Toray Silicone Co Ltd | Organic rubber composition |
| US6326424B1 (en) * | 1998-10-13 | 2001-12-04 | The Goodyear Tire & Rubber Company | Tire tread compound |
| JP2013249359A (en) * | 2012-05-31 | 2013-12-12 | Bridgestone Corp | Rubber composition and tire |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5580919A (en) * | 1995-03-14 | 1996-12-03 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and use in tires |
| US5534592A (en) * | 1995-09-22 | 1996-07-09 | The Goodyear Tire & Rubber Company | High performance blend for tire treads |
| JP4266248B2 (en) | 1999-01-29 | 2009-05-20 | 住友ゴム工業株式会社 | Method for producing rubber composition |
| CN102395473B (en) | 2009-04-29 | 2014-12-17 | 米其林集团总公司 | Tread for heavy vehicle tires |
-
2018
- 2018-01-29 US US16/478,797 patent/US11124632B2/en active Active
- 2018-01-29 EP EP18748405.0A patent/EP3567078A4/en active Pending
- 2018-01-29 JP JP2018530628A patent/JP7024712B2/en active Active
- 2018-01-29 CN CN201880007572.9A patent/CN110234698B/en active Active
- 2018-01-29 WO PCT/JP2018/002609 patent/WO2018143111A1/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6053226A (en) * | 1998-03-13 | 2000-04-25 | The Goodyear Tire & Rubber Company | Rubber composition reinforced with silica and tire with tread thereof |
| US5994448A (en) * | 1998-08-12 | 1999-11-30 | The Goodyear Tire & Rubber Company | High performance tire tread rubber composition |
| US6326424B1 (en) * | 1998-10-13 | 2001-12-04 | The Goodyear Tire & Rubber Company | Tire tread compound |
| JP2001226532A (en) * | 1999-12-08 | 2001-08-21 | Dow Corning Toray Silicone Co Ltd | Organic rubber composition |
| JP2013249359A (en) * | 2012-05-31 | 2013-12-12 | Bridgestone Corp | Rubber composition and tire |
Also Published As
| Publication number | Publication date |
|---|---|
| US20190375920A1 (en) | 2019-12-12 |
| US11124632B2 (en) | 2021-09-21 |
| WO2018143111A1 (en) | 2018-08-09 |
| JPWO2018143111A1 (en) | 2019-11-21 |
| CN110234698A (en) | 2019-09-13 |
| EP3567078A1 (en) | 2019-11-13 |
| EP3567078A4 (en) | 2020-07-22 |
| JP7024712B2 (en) | 2022-02-24 |
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